Fungicidal triazolopyrimidines, methods for producing the same, use thereof for combating harmful fungi and agents containing said substances

ABSTRACT

The invention relates to triazolopyrimidines of formula (I), in which the substituents are defined as follows: L 1  represents cyano, S(═O) n A 1  or C(═O)A 2 , wherein A 1  stands for hydrogen, hydroxy, alkyl, alkylamino or dialkylamino; A 2  stands for C 1 –C 8  alkoxy, C 1 –C 6  haloalkoxy or one of the groups named in A 1 ; and n stands for 0, 1 or 2; L 2 , L 3  represent hydrogen or halogen; L 4 , L 5  represent hydrogen, halogen or alkyl; X represents halogen, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy; R 1  represents alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, alkadienyl, haloalkenyl, cycloalkenyl, alkynyl, haloalkynyl or cycloalkynyl, phenyl, naphthyl, or a five to ten-membered saturated, partially unsaturated or aromatic heterocyclus containing between one and four heteroatoms from the group containing O, N or S; R 2  represents hydrogen or R 1 ; R 1  and R 2  can form, together with the nitrogen atom to which they are bonded, a five or six-membered ring, which can be interrupted and/or substituted by an atom from the group O, N and S; whereby R 1  and/or R 2  can be substituted in accordance with the description. The invention also relates to methods and intermediate products for producing said compounds, to agents containing the latter and to the use of said compounds for combating harmful fungi.

The present invention relates to triazolopyrimidines of the formula I,

in which substituents have the following meanings:

-   -   L¹ is cyano, S(═O)_(n)A¹ or C(═O)A², wherein        -   A¹ is hydrogen, hydroxyl, C₁–C₈-alkyl, C₁–C₈-alkylamino or            di(C₁–C₈-alkyl)amino;        -   A² is C₁–C₈-alkoxy, C₁–C₆-haloalkoxy or one of the groups            mentioned under A¹;        -   n is 0, 1 or 2;    -   L²,L³ are hydrogen or halogen;    -   L⁴,L⁵ are hydrogen, halogen or C₁–C₄-alkyl;    -   X is halogen, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy        or C₁–C₂-haloalkoxy;    -   R¹ is C₁–C₈-alkyl, C₁–C₈-haloalkyl, C₃–C₆-cycloalkyl,        C₃–C₆-halocycloalkyl, C₂–C₈-alkenyl, C₄–C₁₀-alkadienyl,        C₂–C₈-haloalkenyl, C₃–C₆-cycloalkenyl, C₂–C₈-alkynyl,        C₂–C₈-haloalkynyl or C₃–C₆-cycloalkynyl, phenyl, naphthyl, or a        five- to ten-membered saturated, partially unsaturated or        aromatic heterocycle, comprising one to four heteroatoms from        the group consisting of O, N and S;    -   R² is hydrogen or one of the groups mentioned under R¹,        -   R¹ and R² can also, together with the nitrogen atom to which            they are bonded, form a five- or six-membered ring which can            be interrupted by an atom from the group consisting of O, N            and S and/or can carry one or more substituents from the            group consisting of halogen, C₁–C₆-alkyl, C₁–C₆-haloalkyl            and oxy-C₁–C₃-alkylenoxy or in which an N and a neighboring            C atom can be connected via a C₁–C₄-alkylene chain;        -   wherein R¹ and/or R² can be substituted by one to four            identical or different groups R^(a):        -   R^(a) is halogen, cyano, nitro, hydroxyl, C₁–C₆-alkyl,            C₁–C₆-haloalkyl, C₁–C₆-alkylcarbonyl, C₃–C₆-cycloalkyl,            C₁–C₆-alkoxy, C₁–C₆-haloalkoxy, C₁–C₆-alkoxycarbonyl,            C₁–C₆-alkylthio, C₁–C₆-alkylamino, di(C₁–C₆-alkyl)amino,            C₂–C₆-alkenyl, C₂–C₆-alkenyloxy, C₃–C₆-alkynyloxy,            C₃–C₆-cycloalkyl, phenyl, naphthyl or a five- to            ten-membered saturated, partially unsaturated or aromatic            heterocycle, comprising one to four heteroatoms from the            group consisting of O, N and S,            -   wherein these aliphatic, alicyclic or aromatic groups,                for their part, can be partially or completely                halogenated or can carry one to three groups R^(b):            -   R^(b) is halogen, cyano, nitro, hydroxyl, mercapto,                amino, carboxyl, aminocarbonyl, aminothiocarbonyl,                alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy,                alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino,                formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,                alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,                dialkylaminocarbonyl, alkylaminothiocarbonyl or                dialkylaminothiocarbonyl, wherein the alkyl groups in                these radicals comprise 1 to 6 carbon atoms and the                alkenyl or alkynyl groups mentioned in these radicals                comprise 2 to 8 carbon atoms;            -   and/or one to three of the following radicals:        -   cycloalkyl, cycloalkoxy, heterocyclyl or heterocyclyloxy,            wherein the cyclic systems comprise 3 to 10 ring members;            aryl, aryloxy, arylthio, aryl-C₁–C₆-alkoxy,            aryl-C₁–C₆-alkyl, hetaryl, hetaryloxy or hetarylthio,            wherein the aryl radicals preferably comprise 6 to 10 ring            members and the hetaryl radicals comprise 5 or 6 ring            members, wherein the cyclic systems can be partially or            completely halogenated or can be substituted by alkyl or            haloalkyl groups.

The invention relates in addition to processes for and intermediates inthe preparation of these compounds, compositions comprising them andtheir use in the control of harmful fungi.

5–Chlorotriazolopyrimidines for the control of harmful fungi are knownfrom EP-A 71 792, EP-A 550 113, WO-A 98/46608 and WO-A 99/41255.

Fungicidally effective triazolopyrimidines having specific substitutionof the 6-phenyl group are known from EP-A 834 513, WO 98/46607, EP-A 945453, WO 99/48893, U.S. Pat. No. 5,985,883 and WO 02/46195.

However, in many cases, in particular when low amounts are applied,their action is not always satisfactory.

It is the object of the present invention to provide compounds with animproved action and/or a broadened spectrum of activity.

We have found that this object is achieved with the compounds defined atthe start. Processes for and intermediates in their preparation,compositions comprising them and processes for the control of harmfulfungi through the use of the compounds I have also been found.

The compounds of the formula I are distinguished from those from theabovementioned documents in the substitution of the 6-phenyl group,which carries a group L¹ in the para-position, and the substitution ofthe 7-amino group.

The compounds of the formula I have, in comparison with the knowncompounds, an increased activity against harmful fungi. The compoundsaccording to the invention can be obtained in various ways. They areadvantageously prepared by reaction of 5-aminotriazole of the formula IIwith appropriately substituted phenylmalonates of the formula III inwhich R is alkyl, preferably C₁–C₆-alkyl, in particular methyl or ethyl.

This reaction is usually carried out at temperatures of 80° C. to 250°C., preferably 120° C. to 180° C., without solvent or in an inertorganic solvent, in the presence of a base [cf. EP-A 770 615] or in thepresence of acetic acid under the conditions known from Adv. Het. Chem.,Vol. 57, pp. 81ff. (1993).

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons,such as toluene or o-, m- and p-xylene, halogenated hydrocarbons,ethers, nitriles, ketones, alcohols, N-methylpyrrolidone, dimethylsulfoxide, dimethylformamide and dimethylacetamide. In a particularlypreferred way, the reaction is carried out without solvent or inchlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone. Mixturesof the solvents mentioned can also be used.

Suitable bases are generally inorganic compounds, such as alkali metaland alkaline earth metal hydroxides, alkali metal and alkaline earthmetal oxides, alkali metal and alkaline earth metal hydrides, alkalimetal amides, alkali metal and alkaline earth metal carbonates, alkalimetal hydrogencarbonates, or organometallic compounds, in particularalkali metal alkyls, alkyl magnesium halides, and alkali metal andalkaline earth metal alkoxides and magnesium dimethoxide, as well asorganic bases, e.g. tertiary amines, such as trimethylamine,triethylamine, triisopropylethylamine, tributylamine, N-methylpiperidineand N-methylmorpholine, pyridine, substituted pyridines, such ascollidine, lutidine and 4-dimethylaminopyridine, and bicyclic amines.Tertiary amines, such as triisopropylethylamine, tributylamine,N-methylmorpholine or N-methylpiperidine, are especially preferred.

The bases are generally used in catalytic amounts. However, they canalso be used in equimolar amounts, in excess or possibly as solvent.

The starting materials are generally reacted with one another inequimolar amounts. It can be advantageous to the yield to use the baseand the malonate III in an excess with respect to the triazole.

Phenylmalonates of the formula III are advantageously obtained from thereaction of suitably substituted bromobenzenes with dialkyl malonatesunder Cu(I) catalysis [cf. Chemistry Letters, pp. 367–370, 1981; EP-A 1002 788].

The dihydroxytriazolopyrimidines of the formula IV are converted to thedihalopyrimidines of the formula V under the conditions known from WO-A94/20501. A chlorinating agent or a brominating agent, such asphosphorus oxybromide or phosphorus oxychloride, optionally in thepresence of a solvent, is advantageously used as halogenating agent[Hal].

This reaction is usually carried out at 0° C. to 150° C., preferably at80° C. to 125° C. [cf. EP-A 770 615].

Dihalopyrimidines of the formula V are further reacted with amines ofthe formula VI,

in which R¹ and R² are defined as in formula I, to give compounds of theformula I in which X is halogen.

This reaction is advantageously carried out at 0° C. to 70° C.,preferably 10° C. to 35° C., preferably in the presence of an inertsolvent, such as ethers, e.g. dioxane, diethyl ether or, particularly,tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane, andaromatic hydrocarbons, such as, for example, toluene [cf. WO-A98/46608].

The use of a base, such as tertiary amines, for example triethylamine,or inorganic amines, such as potassium carbonate, is preferred; inaddition, excess amine of the formula VI can be used as a base.

Compounds of the formula I in which X represents cyano, C₁–C₆-alkoxy orC₁–C₂-haloalkoxy can advantageously be obtained from the reaction ofcompounds I, in which X represents halogen, preferably chlorine, withcompounds M-X′ (formula VII). Compounds VII represent, depending on themeaning of the group X′ to be introduced, an inorganic cyanide, analkoxide or a haloalkoxide. The reaction is advantageously carried outin the presence of an inert solvent. The cation M in formula VII is oflittle importance; for practical reasons, ammonium, tetraalkylammonium,alkali metal or alkaline earth metal salts are usually preferred.I(X=halogen)+M-X′→I(X═X′)  VII

The reaction temperature usually lies between 0 and 120° C., preferablybetween 10 and 40° C. [cf. J. Heterocycl. Chem., Vol. 12, pp. 861–863(1975)].

Suitable solvents include ethers, such as dioxane, diethyl ether and,preferably, tetrahydrofuran, halogenated hydrocarbons, such asdichloromethane, and aromatic hydrocarbons, such as toluene.

Compounds of the formula I in which X is C₁–C₄-alkyl or C₁–C₄-haloalkylcan advantageously be obtained through the following synthetic route:

The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines IVa are obtained fromthe ketoesters IIIa. The 5-methyl-7-hydroxy-6-phenyltriazolopyrimidinesare obtained through the use of the readily accessible2-phenylacetoacetic esters (IIIa with X¹═CH₃) [cf. Chem. Pharm. Bull.,9, 801, (1961)]. The preparation of the starting compounds IIIa isadvantageously carried out under the conditions described in EP-A 10 02788.

The 5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines obtained in this wayare reacted with halogenating agents [Hal] to give the7-halotriazolopyrimidines of the formula Va. Chlorinating or brominatingagents, such as phosphorus oxybromide, phosphorus oxychloride, thionylchloride, thionyl bromide or sulfuryl chloride, are preferably used. Thereaction can be carried out in bulk or in the presence of a solvent.Usual reaction temperatures are from 0 to 150° C. or, preferably, from80 to 125° C.

The reaction of Va with amines VI is carried out under the conditionsdescribed further above.

Compounds of the formula I in which X represents C₁–C₄-alkyl canalternatively also be prepared from compounds I in which X representshalogen, in particular chlorine, and malonates of the formula VIII. Informula VIII, X″ represents hydrogen or C₁–C₃-alkyl and R representsC₁–C₄-alkyl. They are reacted to give compounds of the formula IX andare decarboxylated to give compounds I [cf. U.S. Pat. No. 5,994,360].

The malonates VIII are known in the literature [J. Am. Chem. Soc., Vol.64, 2714 (1942); J. Org. Chem., Vol. 39, 2172 (1974); Helv. Chim. Acta,Vol. 61, 1565 (1978)] or can be prepared according to the literaturecited.

The subsequent saponification of the ester IX is carried out undergenerally standard conditions. Depending on the various structuralcomponents, the alkaline or the acidic saponification of the compoundsIX may be advantageous. Under the conditions of the saponification ofesters, the decarboxylation to give I may already take place, completelyor partially.

The decarboxylation usually takes place at temperatures of 20° C. to180° C., preferably 50° C. to 120° C., in an inert solvent, optionallyin the presence of an acid.

Suitable acids are hydrochloric acid, sulfuric acid, phosphoric acid,formic acid, acetic acid and p-toluenesulfonic acid. Suitable solventsare water, aliphatic hydrocarbons, such as pentane, hexane, cyclohexaneand petroleum ether, aromatic hydrocarbons, such as toluene and o-, m-and p-xylene, halogenated hydrocarbons, such as methylene chloride,chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropylether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,nitriles, such as acetonitrile and propionitrile, ketones, such asacetone, methyl ethyl ketone, diethyl ketone and tert-butyl methylketone, alcohols, such as methanol, ethanol, n-propanol, isopropanol,n-butanol and tert-butanol, dimethyl sulfoxide, dimethylformamide anddimethylacetamide. In a particularly preferred way, the reaction iscarried out in hydrochloric acid or acetic acid. Mixtures of thesolvents mentioned can also be used.

Compounds of the formula I in which X is C₁–C₄-alkyl can also beobtained by coupling of 5-halotriazolopyrimidines of the formula I inwhich X represents halogen with organometallic reagents of the formulaX. In an embodiment of this process, the reaction is carried out undertransition metal catalysis, such as Ni or Pd catalysis.I(X=halogen)+M ^(Y)(—R ²)_(Y) →I  X

In formula X, M is a metal ion with a valency of Y, such as, forexample, B, Zn or Sn. This reaction can be carried out, for example,analogously to the following methods: J. Chem. Soc. Perkin Trans., 1,1187 (1994), ibid, 1, 2345 (1996); WO-A 99/41255; Aust. J. Chem., Vol.43, 733 (1990); J. Org. Chem., Vol. 43, 358 (1978); J. Chem. Soc. Chem.Commun., 866 (1979); Tetrahedron Lett., Vol. 34, 8267 (1993); ibid, Vol.33, 413 (1992).

If R¹ and R² represent halogen-free groups, optically active amines ofthe formula VI in the (R)-configuration are preferred.

If R¹ or R² comprises haloalkyl or haloalkenyl groups, the(S)-configuration is preferred for optically active amines of theformula VI.

Amines of the formula VI are either commercially available or, if theyhave a center of chirality, are accessible through resolution accordingto WO 02/38565. For example, (R)-3,3-dimethylbut-2-amine (R-DMBA) canparticularly advantageously be prepared in this way.

In a preferred embodiment of the process according to the invention forthe preparation of the compounds in which L¹ represents S(═O)_(n)A¹ withn=1 or 2, the thio compounds with n=0 are oxidized at the formula Istage [Lit.: WO 94/14761; Synth, Commun., Vol. 16, p. 233 (1986)].

Compounds of the formulae I, III and IV in which L¹ is S(═O)_(n)A¹ withn=2 and A¹ is alkyl, in particular methyl, can also be used asintermediates in the preparation of additional6-phenyltriazolopyrimidines. These intermediates can advantageously beused for the preparation of those triazolopyrimidines in which the6-phenyl group exhibits in the para-position a group which can beintroduced as a nucleophile, such as, for example, cyano, nitro,hydroxyl, alkoxy, haloalkoxy or groups bonded via nitrogen, such asalkylamino, dialkylamino or a heterocycle bonded via N [Lit.:Tetrahedron Lett., p. 759 (1967); ibid p. 1763 (2000); J. Org. Chem., p.4705 (1979)]. The exchange of the SO₂ alkyl group with the substituentto be introduced takes place particularly advantageously at the formulaI stage.

Compounds of the formula I in which L¹ is C(═O)A² with A²=hydrogen oralkyl are advantageously prepared from the corresponding compounds inwhich L¹ is CN. This conversion is carried out particularly preferablyat the formula I stage.

Compounds in which L¹ represents CHO are preferably prepared from thecorresponding cyanides by reduction under known conditions [cf. Collect.Czech. Chem. Commun., p. 729 (2000); J. Org. Chem., p. 5298 (2000);Heterocycles, p. 1173 (1987); Chem. Pharm. Bull., p. 1440 (1991)].Compounds in which L¹ represents C(O)alkyl are advantageously obtainedfrom the corresponding cyanides by reaction with Grignard oralkyllithium compounds under known conditions [cf. J. Org. Chem., p.4844 (1994); Synthetic Commun., p. 4067 (1998); Tetrahedron Lett., p.6505 (1988)].

The reaction mixtures are worked up conventionally, e.g. by mixing withwater, separating the phases and possibly chromatographic purificationof the crude products. Some of the intermediates and final products areobtained in the form of colorless or slightly brownish viscous oilswhich, under reduced pressure and at moderately elevated temperature,are freed or purified from volatile constituents. If the intermediatesand final products are obtained as solids, the purification can alsotake place by recrystallization or trituration.

If individual compounds I are not accessible by the methods describedabove, they can be prepared by derivatization of other compounds I.

If isomeric mixtures are obtained in the synthesis, a separation is,however, generally not absolutely necessary, since the individualisomers can sometimes be converted into one another during preparationfor application or upon application (e.g., under the effect of light,acid or bases). Corresponding conversions can also take place afterapplication, for example, in the treatment of plants, in the treatedplant or in the harmful fungus to be controlled.

Collective terms were used in the definitions of the symbols given inthe above formulae, which collective terms are generally representativeof the following substituents:

-   halogen: fluorine, chlorine, bromine and iodine;-   alkyl: saturated, straight-chain or branched hydrocarbon radicals    with 1 to 4, 6 or 8 carbon atoms, e.g. C₁–C₆-alkyl, such as methyl,    ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,    1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,    3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,    1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,    2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,    1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,    2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,    1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl    and 1-ethyl-2-methylpropyl;-   haloalkyl: straight-chain or branched alkyl groups with 1 to 8    carbon atoms (as mentioned above), in which the hydrogen atoms in    these groups can be partially or completely replaced by halogen    atoms as mentioned above, e.g. C₁–C₂-haloalkyl, such as    chloromethyl, bromomethyl, dichloromethyl, trichloromethyl,    fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,    dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,    1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,    2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,    2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,    2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;-   alkenyl: unsaturated, straight-chain or branched hydrocarbon    radicals with 2 to 4, 6 or 8 carbon atoms and a double bond in any    position, e.g. C₂–C₆-alkenyl, such as ethenyl, 1-propenyl,    2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,    1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,    2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,    1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,    1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,    1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,    1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,    1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,    1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,    1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,    4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,    3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,    2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,    1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,    4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,    1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,    1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,    1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,    2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,    2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,    3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,    1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,    2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,    1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and    1-ethyl-2-methyl-2-propenyl;-   haloalkenyl: unsaturated, straight-chain or branched hydrocarbon    radicals with 2 to 8 carbon atoms and a double bond in any position    (as mentioned above), in which the hydrogen atoms in these groups    can be partially or completely replaced by halogen atoms as    mentioned above, in particular fluorine, chlorine and bromine;-   alkynyl: straight-chain or branched hydrocarbon groups with 2 to 4,    6 or 8 carbon atoms and a triple bond in any position, e.g.    C₂–C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,    2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl,    3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl,    2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl,    1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,    5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,    1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,    3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl,    4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,    1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,    3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,    2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;-   haloalkynyl: unsaturated, straight-chain or branched hydrocarbon    radicals with 2 to 8 carbon atoms and a triple bond in any position    (as mentioned above), in which the hydrogen atoms in these groups    can be partially or completely replaced by halogen atoms as    mentioned above, in particular fluorine, chlorine and bromine;-   cycloalkyl: saturated mono- or bicyclic hydrocarbon groups with 3 to    6 or 8 carbon ring members, e.g. C₃–C₈-cycloalkyl, such as    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and    cyclooctyl;-   alkoxycarbonyl: an alkoxy group with 1 to 6 carbon atoms (as    mentioned above) which is bonded to the backbone via a carbonyl    group (—CO—);-   oxyalkylenoxy: unbranched divalent chains formed from 1 to 3 CH₂    groups in which both valencies is bonded to the backbone via an    oxygen atom, e.g. OCH₂O, OCH₂CH₂O and OCH₂CH₂CH₂O;-   five- to ten-membered saturated, partially unsaturated or aromatic    heterocycle comprising one to four heteroatoms from the group    consisting of O, N and S:    -   5- or 6-membered heterocyclyl comprising one to three nitrogen        atoms and/or one oxygen or sulfur atom or one or two oxygen        and/or sulfur atoms, e.g. 2-tetrahydrofuranyl,        3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,        2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,        4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl,        4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl,        4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl,        4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,        4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl,        4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,        1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,        1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,        1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,        1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl,        2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,        2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,        2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl,        2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,        2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,        2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,        2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,        2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,        2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,        2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,        2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,        2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,        2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,        3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,        3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,        4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,        4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl,        2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,        2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,        3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,        3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,        3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,        3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl,        2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,        3-hexahydropyridazinyl, 4-hexahydropyridazinyl,        2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl,        5-hexahydropyrimidinyl, 2-piperazinyl,        1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;    -   5-membered heteroaryl comprising one to four nitrogen atoms or        one to three nitrogen atoms and one sulfur or oxygen atom:        5-ring heteroaryl groups which, in addition to carbon atoms, can        comprise one to four nitrogen atoms or one to three nitrogen        atoms and one sulfur or oxygen atom as ring members, e.g.        2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,        3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,        4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl,        5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,        4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,        1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,        1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,        1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl        and 1,3,4-triazol-2-yl;    -   6-membered heteroaryl comprising one to three or one to four        nitrogen atoms: 6-ring heteroaryl groups which, in addition to        carbon atoms, can comprise one to three or one to four nitrogen        atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl,        4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,        4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl        and 1,2,4-triazin-3-yl;-   alkylene: unbranched divalent chains formed from 3 to 5 CH₂ groups,    e.g. CH₂, CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂ and CH₂CH₂CH₂CH₂CH₂;-   oxyalkylene: unbranched divalent chains formed from 2 to 4 CH₂    groups in which one valency is bonded to the backbone via an oxygen    atom, e.g. OCH₂CH₂, OCH₂CH₂CH₂ and OCH₂CH₂CH₂CH₂;-   oxyalkylenoxy: unbranched divalent chains formed from 1 to 3 CH₂    groups in which both valencies is bonded to the backbone via an    oxygen atom, e.g. OCH₂O, OCH₂CH₂O and OCH₂CH₂CH₂O.

The (R)- and (S)-isomers and the racemates of compounds of the formula Iwhich have chiral centers are included in the present invention.

The embodiments of the intermediates which are especially preferred withregard to the variables correspond to those of the radicals L¹, L², L³,L⁴, L⁵, R¹, R² and X of the formula I.

In view of their intended use of the triazolopyrimidines of the formulaI, the following meanings of the substituents, in each case alone or incombination, are especially preferred:

Preference is given to compounds I in which R¹ is C₁–C₆-alkyl orC₁–C₈-haloalkyl.

Preference is also given to compounds I in which R¹ is C₂–C₁₀-alkenyl orC₂–C₁₀-alkynyl.

Preference is similarly given to compounds I in which R¹ is a saturatedor aromatic 5- or 6-membered heterocycle.

Compounds I are particularly preferred in which R¹ is a group B

in which

-   Y¹ represents hydrogen, fluorine or C₁–C₆-fluoroalkyl,-   Y² represents hydrogen or fluorine, or Y¹ and Y² together form a    double bond;-   m is 0 or 1; and-   R³ represents hydrogen or methyl.

Preference is furthermore given to compounds I in which R¹ isC₃–C₆-cycloalkyl which can be substituted by C₁–C₄-alkyl.

Preference is particularly given to compounds I in which R² representshydrogen.

Similarly preferred are compounds I in which R² is methyl or ethyl.

If R¹ and/or R² represent halogen-free groups with a center ofchirality, the (R)-isomers are preferred. If R¹ and/or R² comprisehaloalkyl or haloalkenyl groups with a center of chirality, the(S)-isomers are preferred.

Furthermore, particular preference is given to compounds I in which R¹and R², together with the nitrogen atom to which they are bonded, form afive- or six-membered ring which can be interrupted by an atom from thegroup consisting of O, N and S and/or can carry one or more substituentsfrom the group consisting of halogen, C₁–C₆-alkyl, C₁–C₆-haloalkyl andoxy-C₁–C₃-alkylenoxy or in which an N and a neighboring C atom can beconnected via a C₁–C₄-alkylene chain.

Particularly preferred are compounds I in which R¹ and R², together withthe nitrogen atom to which they are bonded, form a 5- or 6-membered ringwhich optionally can exhibit a double bond and can be substituted asdescribed above.

Particular preference is given in particular to compounds I in which R¹and R², together with the nitrogen atom to which they are bonded, form apiperidine, morpholine or thiomorpholine ring, in particular apiperidinyl ring, which is optionally substituted by one to threehalogen, C₁–C₄-alkyl or C₁–C₄-haloalkyl groups, in particular by4-methyl.

Particularly preferred are furthermore compounds I in which R¹ and R²,together with the nitrogen atom to which they are bonded, form apyrrolidine ring which is optionally substituted by one or two halogen,C₁–C₄-alkyl or C₁–C₄-haloalkyl groups, in particular by 2-methyl.

Preferred are compounds of the formula I in which at least one L² and/orL³ group does not represent hydrogen.

In addition, compounds of the formula I are preferred in which L¹represents S(═O)_(n)A¹, L² represents halogen, L³ and L⁴ representhydrogen or halogen and L⁵ represents hydrogen. They are denoted ascompounds I.1.

Similarly preferred are compounds I.1 in which A¹ represents hydrogenor, in particular, methyl.

Preference is given in particular to compounds I.1 in which n=0.

Preference is given to compounds I.1 in which both L² and L³ representhalogen, in particular fluorine. Furthermore preferred are the compoundsI.1 in which L² represents fluorine and L³ represents chlorine or L² andL³ both represent chlorine. L⁴ preferably represents hydrogen.

An additional preferred embodiment of the compounds of the formula I arethose in which L¹ represents cyano or C(═O)A². They are denoted ascompounds I.2.

Particular preference is furthermore given to compounds I.2 in which L¹represents C₁–C₆-alkoxycarbonyl.

Similarly particularly preferred are compounds I.2 in which L²represents halogen and L³ represents halogen or hydrogen, in particularhalogen.

Particular preference is also given to compounds I.2 in which L⁴represents hydrogen and L⁵ represents hydrogen or methyl.

Preference is given in particular to compounds of the formulae IA and IBin which the variables have the meanings given for formula I:

Preference is furthermore given to compounds IC:

Preference is also given, in addition, to compounds I.2 in which L¹represents C(═O)OCH₃, L² represents fluorine, L³ and L⁵ representhydrogen and L⁴ represents methyl.

Particular preference is given to compounds I in which X representschlorine.

Particular preference is given, in view of their use, to the compounds Icompiled in the following tables. The groups mentioned in the tables fora substituent additionally represent, considered per se, independentlyof the combination in which they are mentioned, a particularly preferredembodiment of the substituent in question.

Table 1

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylthio, L² and L³ represent fluorine and L⁴ representshydrogen and the combination of R¹ and R² for a compound each timecorresponds to a row of table A.

Table 2

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfinyl, L² and L³ represent fluorine and L⁴represents hydrogen and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 3

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfonyl, L² and L³ represent fluorine and L⁴represents hydrogen and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 4

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylthio, L² represents fluorine, L³ represents chlorineand L⁴ represents hydrogen and the combination of R¹ and R² for acompound each time corresponds to a row of table A.

Table 5

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfinyl, L² represents fluorine, L³ representschlorine and L⁴ represents hydrogen and the combination of R¹ and R² fora compound each time corresponds to a row of table A.

Table 6

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfonyl, L² represents fluorine, L³ representschlorine and L⁴ represents hydrogen and the combination of R¹ and R² fora compound each time corresponds to a row of table A.

Table 7

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylthio, L² and L³ represent chlorine and L⁴ representshydrogen and the combination of R¹ and R² for a compound each timecorresponds to a row of table A.

Table 8

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfinyl, L² and L³ represent chlorine and L⁴represents hydrogen and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 9

Compounds of the formula I.1 in which X represents chlorine, L¹represents methylsulfonyl, L² and L³ represent chlorine and L⁴represents hydrogen and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 10

Compounds of the formula IA in which X is chlorine, L¹ is C(═O)OCH₃ andL² and L³ are fluorine and the combination of R¹ and R² for a compoundeach time corresponds to a row of table A.

Table 11

Compounds of the formula IA in which X is chlorine, L¹ is cyano and L²and L³ are fluorine and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 12

Compounds of the formula IA in which X is chlorine, L¹ is CHO and L² andL³ are fluorine and the combination of R¹ and R² for a compound eachtime corresponds to a row of table A.

Table 13

Compounds of the formula IA in which X is chlorine, L¹ is C(═O)CH₃ andL² and L³ are fluorine and the combination of R¹ and R² for a compoundeach time corresponds to a row of table A.

Table 14

Compounds of the formula IA in which X is chlorine, L¹ is C(═O)NHCH₃ andL² and L³ are [lacuna] and the combination of R¹ and R² for a compoundeach time corresponds to a row of table A.

Table 15

Compounds of the formula IB in which X is chlorine, L¹ is C(═O)OCH₃ andL² is fluorine and the combination of R¹ and R² for a compound each timecorresponds to a row of table A.

Table 16

Compounds of the formula IB in which X is chlorine, L¹ is C(═O)OCH₃ andL² is chlorine and the combination of R¹ and R² for a compound each timecorresponds to a row of table A.

Table 17

Compounds of the formula IC in which X is chlorine and L¹ is C(═O)OCH₃and the combination of R¹ and R² for a compound each time corresponds toa row of table A.

Table 18

Compounds of the formula IC in which X is chlorine and L¹ is cyano andthe combination of R¹ and R² for a compound each time corresponds to arow of table A.

Table 19

Compounds of the formula I in which X is chlorine, L¹ is C(═O)OCH₃, andL², L³, L⁴ and L⁵ are fluorine and the combination of R¹ and R² for acompound each time corresponds to a row of table A.

TABLE A No. R¹ R² A-1 CH₂CH₃ H A-2 CH₂CH₃ CH₃ A-3 CH₂CH₃ CH₂CH₃ A-4CH₂CF₃ H A-5 CH₂CF₃ CH₃ A-6 CH₂CF₃ CH₂CH₃ A-7 CH₂CCl₃ H A-8 CH₂CCl₃ CH₃A-9 CH₂CCl₃ CH₂CH₃ A-10 CH₂CH₂CH₃ H A-11 CH₂CH₂CH₃ CH₃ A-12 CH₂CH₂CH₃CH₂CH₃ A-13 CH₂CH₂CH₃ CH₂CH₂CH₃ A-14 CH(CH₃)₂ H A-15 CH(CH₃)₂ CH₃ A-16CH(CH₃)₂ CH₂CH₃ A-17 (±) CH(CH₃)—CH₂CH₃ H A-18 (±) CH(CH₃)—CH₂CH₃ CH₃A-19 (±) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-20 (S) CH(CH₃)—CH₂CH₃ H A-21 (S)CH(CH₃)—CH₂CH₃ CH₃ A-22 (S) CH(CH₃)—CH₂CH₃ CH₂CH₃ A-23 (R)CH(CH₃)—CH₂CH₃ H A-24 (R) CH(CH₃)—CH₂CH₃ CH₃ A-25 (R) CH(CH₃)—CH₂CH₃CH₂CH₃ A-26 (±) CH(CH₃)—CH(CH₃)₂ H A-27 (±) CH(CH₃)—CH(CH₃)₂ CH₃ A-28(±) CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-29 (S) CH(CH₃)—CH(CH₃)₂ H A-30 (S)CH(CH₃)—CH(CH₃)₂ CH₃ A-31 (S) CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-32 (R)CH(CH₃)—CH(CH₃)₂ H A-33 (R) CH(CH₃)—CH(CH₃)₂ CH₃ A-34 (R)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-35 (±) CH(CH₃)—C(CH₃)₃ H A-36 (±)CH(CH₃)—C(CH₃)₃ CH₃ A-37 (±) CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-38 (S)CH(CH₃)—C(CH₃)₃ H A-39 (S) CH(CH₃)—C(CH₃)₃ CH₃ A-40 (S) CH(CH₃)—C(CH₃)₃CH₂CH₃ A-41 (R) CH(CH₃)—C(CH₃)₃ H A-42 (R) CH(CH₃)—C(CH₃)₃ CH₃ A-43 (R)CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-44 (±) CH(CH₃)—CF₃ H A-45 (±) CH(CH₃)—CF₃ CH₃A-46 (±) CH(CH₃)—CF₃ CH₂CH₃ A-47 (S) CH(CH₃)—CF₃ H A-48 (S) CH(CH₃)—CF₃CH₃ A-49 (S) CH(CH₃)—CF₃ CH₂CH₃ A-50 (R) CH(CH₃)—CF₃ H A-51 (R)CH(CH₃)—CF₃ CH₃ A-52 (R) CH(CH₃)—CF₃ CH₂CH₃ A-53 (±) CH(CH₃)—CCl₃ H A-54(±) CH(CH₃)—CCl₃ CH₃ A-55 (±) CH(CH₃)—CCl₃ CH₂CH₃ A-56 (S) CH(CH₃)—CCl₃H A-57 (S) CH(CH₃)—CCl₃ CH₃ A-58 (S) CH(CH₃)—CCl₃ CH₂CH₃ A-59 (R)CH(CH₃)—CCl₃ H A-60 (R) CH(CH₃)—CCl₃ CH₃ A-61 (R) CH(CH₃)—CCl₃ CH₂CH₃A-62 CH₂CF₂CF₃ H A-63 CH₂CF₂CF₃ CH₃ A-64 CH₂CF₂CF₃ CH₂CH₃ A-65CH₂(CF₂)₂CF₃ H A-66 CH₂(CF₂)₂CF₃ CH₃ A-67 CH₂(CF₂)₂CF₃ CH₂CH₃ A-68CH₂C(CH₃)═CH₂ H A-69 CH₂C(CH₃)═CH₂ CH₃ A-70 CH₂C(CH₃)═CH₂ CH₂CH₃ A-71CH₂CH═CH₂ H A-72 CH₂CH═CH₂ CH₃ A-73 CH₂CH═CH₂ CH₂CH₃ A-74 CH(CH₃)CH═CH₂H A-75 CH(CH₃)CH═CH₂ CH₃ A-76 CH(CH₃)CH═CH₂ CH₂CH₃ A-77CH(CH₃)C(CH₃)═CH₂ H A-78 CH(CH₃)C(CH₃)═CH₂ CH₃ A-79 CH(CH₃)C(CH₃)═CH₂CH₂CH₃ A-80 cyclopentyl H A-81 cyclopentyl CH₃ A-82 cyclopentyl CH₂CH₃A-83 cyclohexyl H A-84 cyclohexyl CH₃ A-85 cyclohexyl CH₂CH₃ A-86—(CH₂)₂CH═CHCH₂— A-87 —(CH₂)₂C(CH₃)═CHCH₂— A-88 —(CH₂)₂CH(CH₃)(CH₂)₂—A-89 —(CH₂)₂CHF(CH₂)₂— A-90 —(CH₂)₃CHFCH₂— A-91 —(CH₂)₂CH(CF₃)(CH₂)₂—A-92 —(CH₂)₂O(CH₂)₂— A-93 —(CH₂)₂S(CH₂)₂— A-94 —(CH₂)_(5—) A-95—(CH₂)_(4—) A-96 —CH₂CH═CHCH₂— A-97 —CH(CH₃)(CH₂)₃— A-98—CH₂CH(CH₃)(CH₂)₂—

The compounds I are suitable as fungicides. They are distinguished by anoutstanding effectiveness against a broad spectrum of phytopathogenicfungi, especially from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some are systemically effective andthey can be used in plant protection as foliar and soil fungicides.

They are particularly important in the control of a multitude of fungion various cultivated plants, such as wheat, rye, barley, oats, rice,maize, grass, bananas, cotton, soya, coffee, sugar cane, vines, fruitsand ornamental plants, and vegetables, such as cucumbers, beans,tomatoes, potatoes and cucurbits, and on the seeds of these plants.

They are especially suitable for controlling the following plantdiseases:

-   Alternaria species on fruit and vegetables,-   Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental    plants and grapevines,-   Cercospora arachidicola on peanuts,-   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,-   Blumeria graminis (powdery mildew) on cereals,-   Fusarium and Verticillium species on various plants,-   Helminthosporium species on cereals,-   Mycosphaerella species on bananas and peanuts,-   Phytophthora infestans on potatoes and tomatoes,-   Plasmopara viticola on grapevines,-   Podosphaera leucotricha on apples,-   Pseudocercosporella herpotrichoides on wheat and barley,-   Pseudoperonospora species on hops and cucumbers,-   Puccinia species on cereals,-   Pyricularia oryzae on rice,-   Rhizoctonia species on cotton, rice and lawns,-   Septoria nodorum on wheat,-   Uncinula necator on grapevines,-   Ustilago species on cereals and sugar cane, and-   Venturia species (scab) on apples and pears.

The compounds I are also suitable for controlling harmful fungi, such asPaecilomyces variotii, in the protection of materials (e.g. wood, paper,paint dispersions, fibers or fabrics) and in the protection of storedproducts.

The compounds I are employed by treating the fungi or the plants, seeds,materials or soil to be protected from fungal attack with a fungicidallyeffective amount of the active compounds. The application can be carriedout both before and after the infection of the materials, plants orseeds by the fungi. The fungicidal compositions generally comprisebetween 0.1 and 95%, preferably between 0.5 and 90%, by weight of activecompound.

When employed in plant protection, the amounts applied are, depending onthe kind of effect desired, between 0.01 and 2.0 kg of active compoundper ha.

In seed treatment, amounts of active compound of 0.001 to 0.1 g,preferably 0.01 to 0.05 g, per kilogram of seed are generally necessary.

When used in the protection of materials or stored products, the amountof active compound applied depends on the kind of application area andon the effect desired. Amounts customarily applied in the protection ofmaterials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg,of active compound per cubic meter of treated material.

The compounds I can be converted to the usual formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The application form depends on the respective use intended; it shouldin any case guarantee a fine and uniform distribution of the compoundaccording to the invention.

The formulations are prepared in a known way, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible, when water is thediluent, also to use other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are essentially: solvents, such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol),ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers, such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic ores (e.g.highly dispersed silicic acid, silicates); emulsifiers, such as nonionicand anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants, such aslignosulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid and dibutylnaphthalensulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids, andalkali metal and alkaline earth metal salts thereof, salts of sulfatedfatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or of naphthalenesulfonic acid with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycolethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignosulfite waste liquors and methylcellulose.

Petroleum fractions having medium to high boiling points, such askerosene or diesel fuel, furthermore coal tar oils, and oils ofvegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons,e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes or derivatives thereof, methanol, ethanol,propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol,cyclohexanone, chlorobenzene or isophorone, or highly polar solvents,e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone orwater, are suitable for the preparation of directly sprayable solutions,emulsions, pastes or oil dispersions.

Powders, combinations for broadcasting and dusts can be prepared bymixing or mutually grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active compounds to solidcarriers. Solid carriers are, e.g., mineral earths, such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, e.g.,ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, andplant products, such as cereal meal, tree bark meal, wood meal andnutshell meal, cellulose powders and other solid carriers.

The formulations generally comprise between 0.01 and 95% by weight,preferably between 0.1 and 90% by weight, of the active compound. Theactive compounds are employed therein in a purity of 90% to 100%,preferably 95% to 100% (according to the NMR spectrum).

Examples for formulations are:

-   I. 5 parts by weight of a compound according to the invention are    intimately mixed with 95 parts by weight of finely divided kaolin.    In this way, a dust comprising 5% by weight of the active compound    is obtained.-   II. 30 parts by weight of a compound according to the invention are    intimately mixed with a mixture of 92 parts by weight of pulverulent    silica gel and 8 parts by weight of liquid paraffin, which had been    sprayed onto the surface of this silica gel. In this way, an active    compound preparation with good adhesive properties (active compound    content 23% by weight) is obtained.-   III. 10 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 90 parts by weight of xylene, 6    parts by weight of the addition product of 8 to 10 mol of ethylene    oxide with 1 mol of the N-monoethanolamide of oleic acid, 2 parts by    weight of the calcium salt of dodecylbenzenesulfonic acid and 2    parts by weight of the addition product of 40 mol of ethylene oxide    with 1 mol of castor oil (active compound content 9% by weight).-   IV. 20 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 60 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight    of the addition product of 7 mol of ethylene oxide with 1 mol of    isooctylphenol and 5 parts by weight of the addition product of 40    mol of ethylene oxide with 1 mol of castor oil (active compound    content 16% by weight).-   V. 80 parts by weight of a compound according to the invention are    intimately mixed with 3 parts by weight of the sodium salt of    diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    7 parts by weight of pulverulent silica gel and are ground in a    hammer mill (active compound content 80% by weight).-   VI. 90 parts by weight of a compound according to the invention are    mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a    solution is obtained which is suitable for use in the form of very    small drops (active compound content 90% by weight).-   VII. 20 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 40 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight    of the addition product of 7 mol of ethylene oxide with 1 mol of    isooctylphenol and 10 parts by weight of the addition product of 40    mol of ethylene oxide with 1 mol of castor oil. By running the    solution into 100 000 parts by weight of water and finely dispersing    it therein, an aqueous dispersion is obtained comprising 0.02% by    weight of the active compound.-   VIII. 20 parts by weight of a compound according to the invention    are intimately mixed with 3 parts by weight of the sodium salt of    diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    60 parts by weight of pulverulent silica gel and are ground in a    hammer mill. A spray emulsion comprising 0.1% by weight of the    active compound is obtained by fine dispersion of the mixture in 20    000 parts by weight of water.

The active compounds can be used as such, in the form of theirformulations or of the application forms prepared therefrom, e.g. in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dusts, compositions forbroadcasting or granules, by spraying, atomizing, dusting, broadcastingor watering. The application forms depend entirely on the intended uses;they should in any case guarantee the finest possible dispersion of theactive compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates,pastes or wettable powders (spray powders, oil dispersions) by additionof water. To prepare emulsions, pastes or oil dispersions, thesubstances can be homogenized in water, as such or dissolved in an oilor solvent, by means of wetting agents, tackifiers, dispersants oremulsifiers. However, concentrates comprising active substance, wettingagent, tackifier, dispersant or emulsifier and possibly solvent or oilcan also be prepared, which concentrates are suitable for dilution withwater.

The concentrations of active compound in the ready-for-use preparationscan be varied within relatively wide ranges. In general, they arebetween 0.0001 and 10%, preferably between 0.01 and 1%.

The active compounds can also be used with great success in the ultralow volume (ULV) process, it being possible to apply formulations withmore than 95% by weight of active compound or even the active compoundwithout additives.

Oils of various types, herbicides, fungicides, other pesticides andbactericides can be added to the active compounds, if need be also notuntil immediately before use (tank mix). These agents can be added tothe compositions according to the invention in a weight ratio of 1:10 to10:1.

The compositions according to the invention can, in the application formas fungicides, also be present together with other active compounds,which e.g. with herbicides, insecticides, growth regulators, fungicidesor also with fertilizers. On mixing the compounds I or the compositionscomprising them in the application form as fungicides with otherfungicides, in many cases an expansion of the fungicidal spectrum ofactivity is obtained.

The following list of fungicides, with which the compounds according tothe invention can be used in conjunction, is intended to illustrate thepossible combinations but does not limit them:

-   sulfur, dithiocarbamates and their derivatives, such as iron(III)    dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc    ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,    manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram    disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),    ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc    (N,N′-propylenebisdithiocarbamate) or    N,N′-polypropylenebis(thiocarbamoyl)disulfide;-   nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate,    2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,    2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate or diisopropyl    5-nitroisophthalate;-   heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,    2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide,    2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl    phthalimidophosphonothioate,    5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,    2,3-dicyano-1,4-dithioanthraquinone,    2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl    1-(butylcarbamoyl)-2-benzimidazolecarbamate,    2-(methoxycarbonylamino)benzimidazole, 2-(2-furyl)benzimidazole,    2-(4-thiazolyl)benzimidazole,    N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,    N-(trichloromethylthio)tetrahydrophthalimide or    N-(trichloromethylthio)phthalimide,-   N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide,    5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,    2-thiocyanatomethylthiobenzothiazole,    1,4-dichloro-2,5-dimethoxybenzene,    4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine    1-oxide, 8-hydroxyquinoline or its copper salt,    2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,    2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 4,4-dioxide,    2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,    2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,    2,4,5-trimethylfuran-3-carboxanilide,    N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,    N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,    2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine    2,2,2-trichloroethyl acetal,    piperazin-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,    1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,    2,6-dimethyl-N-tridecylmorpholine or its salts,    2,6-dimethyl-N-cyclododecylmorpholine or its salts,    N-[3-(p-(tert-butyl)phenyl)-2-methylpropyl]-cis-2,6-dimethyl-morpholine,    N-[3-(p-(tert-butyl)phenyl)-2-methyl propyl]piperidine,    1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,    1-[2-(2,4-dichlorophenyl)-4-(n-propyl)-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,    N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,    1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,    1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,    (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,    α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,    5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,    bis(p-chlorophenyl)-3-pyridinemethanol,    1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene or    1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,-   strobilurins, such as methyl    E-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, methyl    E-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,    methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]-acetamide,    methyl-E-methoxyimino[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,    methyl    E-2-{2-[2-trifluoromethylpyrid-6-yl]oxymethyl]phenyl}-3-methoxyacrylate,    methyl(E,E)-methoxy    imino{2-[1-(3-trifluoromethylphenyl)ethylideneaminooxymethyl]phenyl}acetate    or methyl    N-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxycarbamate,-   anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2-yl)aniline,    N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline or    N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,-   phenylpyrroles, such as    4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,-   cinnamamides, such as    3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine or    3-(4-fluorophenyl-3-(3,4-dimethoxyphenyl)acryloylmorpholine,-   and various fungicides, such as dodecylguanidine acetate,    1-(3-bromo-6-methoxy-2-methylphenyl)-1-(2,3,4-trimethoxy-6-methylphenyl)methanone,    3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl glutarimide,    hexachlorobenzene, methyl    N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,    N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-DL-alanine methyl    ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyro-lactone,    N-(2,6-dimethylphenyl)-N-(phenylacetyl)-DL-alanine methyl ester,    5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,    3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,    3-(3,5-dichlorophenyl)-1-isopropylcarba-moylhydantoin,    N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,    2-cyano-[N-(ethylaminocarbonyl)-2-methoxyimino]acetamide,    1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,    2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,    N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,    1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole,    5-chloro-2-cyano-4-(p-tolyl)imidazole-1-sulfonic acid dimethylamide    or    3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide.

SYNTHESIS EXAMPLES

The procedures described in the following synthesis examples were usedto prepare further compounds I by appropriate modification of thestarting compounds. The compounds thus obtained are listed in thefollowing table, together with physical data.

Example 1 Preparation of Diethyl 4-cyanophenylmalonate

Diethyl malonate (0.49 mol) was added at approximately 60° C. over 2hours to a suspension of sodium hydride (0.51 mol) in 140 ml of1,4-dioxane. After stirring for a further 10 min, 0.05 mol of CuBr wereadded. After 15 min, 0.25 mol of 4-cyanobromobenzene in 10 ml of dioxanewere added. The reaction mixture was maintained at 100° C. forapproximately 14 hours and then, at approximately 15° C., 35 ml of 12Nhydrochloric acid were slowly added. The precipitate was filtered offand the filtrate was extracted with diethyl ether. After phaseseparation, the organic phase was dried and then freed from the solvent.32 g of the title compound remained.

Example 2 Preparation of5,7-dihydroxy-6-(4-cyanophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 14 g of 3-amino-1,2,4-triazole, 0.17 mol of the ester fromexample 1 and 50 ml of tributylamine (50 ml) was stirred at 180° C. forapproximately 6 hours. A solution of 21 g of NaOH in 200 ml of water wasadded at approximately 700 and the mixture was stirred for a further 30min. The organic phase was separated and the aqueous phase was extractedwith diethyl ether. The product precipitated from the aqueous phaseafter acidification with concentrated hydrochloric acid. 28 g of thetitle compound were obtained by filtration.

Example 3 Preparation of5,7-dichloro-6-(4-cyanophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 25 g of the triazolopyrimidine from example 2 and 50 ml ofPOCl₃ was refluxed for 8 hours, POCl₃ being distilled off. The residuewas added to a CH₂Cl₂-water mixture and the organic phase was separated,washed, dried and then freed from the solvent. 23 g of the titlecompound were obtained.

Example 4 Preparation of5-chloro-6-(4-cyanophenyl)-7-isopropylamino-[1,2,4]triazolo[1,5-a]pyrimidine [I-1]

A solution of 1.5 mmol of isopropylamine and 1.5 mmol of triethylaminein 10 ml of dichloromethane was added with stirring to a solution of 1.5mmol of the product from ex. 3 in 20 ml of dichloromethane. The reactionmixture was stirred at 20 to 25° C. for approximately 16 hours and thenwashed with dilute hydrochloric acid. The organic phase was separated,dried and freed from the solvent. After chromatography on silica gel,330 mg of the title compound with a melting point of 190° C. wereobtained.

Example 5 Preparation of5,7-dihydroxy-6-(2,6-difluoro-4-thiomethylphenyl)-[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 3-amino-1,2,4-triazole (14 g),diethyl(2,6-difluoro-4-(thiomethyl)phenyl)malonate (0.17 mol) andtributylamine (50 ml) was heated at 180° C. for approximately 6 hours.After cooling the reaction mixture to 70° C., the solution was treatedwith 21 g of NaOH in 200 ml of water and stirred for a further 30 min.After separating the organic phase and extracting the aqueous phase withdiethyl ether, the title compound was precipitated from the aqueousphase by acidification with concentrated HCl solution. 37 g wereisolated.

Example 6 Preparation of5,7-dichloro-6-(2,6-difluoro-4-(thiomethyl)phenyl)-[1,2,4]triazolo1,5-a]pyrimidine

A mixture of5,7-dihydroxy-6-(2,6-difluoro-4-(thiomethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine(30 g, Ex. 5) and 50 ml of POCl₃ was refluxed for approximately eighthours; some POCl₃ was distilled off in the process. The residue wasadded to a CH₂Cl₂/water mixture. The organic phase was separated, driedand freed from the solvent. 21 g of the title compound with a meltingpoint of 138° C. remained behind.

Example 7 Preparation of5-chloro-6-(2,6-difluoro-4-(thiomethyl)phenyl)-7-(1,1,1-trifluoroprop-2-yl)amino-[1,2,4]triazolo[1,5-a]pyrimidine[1–6]

A solution of 6 mmol of5,7-dichloro-6-(2,6-difluoro-4-(thiomethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine(Ex. 6) in 20 ml of dichloromethane was treated, with stirring, with asolution of 6 mmol of 1,1,1-trifluoro-2-aminopropane and 6 mmol oftriethylamine in 40 ml of dichloromethane. The solution was stirred at20–25° C. for approximately 16 hours and then was washed with dilute HClsolution. The organic phase was separated, dried and freed from thesolvent. After chromatography on silica gel, 1.2 g of the title compoundwith a melting point of 174° C. were obtained from the residue.

Example 8 Preparation of5-chloro-6-(2,6-difluoro-4-(methylsulfonyl)phenyl)-7-(1,1,1-trifluoroprop-2-yl)amino-[1,2,4]triazolo[1,5-a]pyrimidine(8a) and5-chloro-6-(2,6-difluoro-4-(methylsulfinyl)phenyl)-7-(1,1,1-trifluoroprop-2-yl)amino-[1,2,4]triazolo[1,5-a]pyrimidine(8b)

A solution of 3 mmol of5-chloro-6-(2,6-difluoro-4-(thiomethyl)phenyl)-7-(1,1,1-trifluoroprop-2-yl)amino-[1,2,4]triazolo[1,5-a]pyrimidine(Ex. 7) in 20 ml of dichloromethane was treated with 0.13 g of ammoniummolybdate and 0.22 ml of 98% formic acid. 9 mmol of H₂O₂ were added andthen the reaction mixture was stirred at 20–25° C. for 24 hours. Thereaction mixture was added to water and the organic phase was separated,washed with 10% NaHSO₃ solution, dried and freed from the solvent. Afterchromatography on silica gel, 0.28 g of the sulfone (8a) with a meltingpoint of 211° C. and 0.39 g of the sulfoxide (8b) with a melting pointof 264° C. were obtained.

Example 9 Preparation of5-cyano-6-(2,6-difluoro-4-cyanophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 0.1 mol of5-chloro-6-(2,6-difluoro-4-cyanophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]-triazolo-[1,5-a]-pyrimidine(No. I-5) and 0.25 mol of tetraethylammonium cyanide in 750 ml ofdimethylformamide (DMF) was stirred at 20–25° C. for 16 hours. Afteraddition of water and methyl tert-butyl ether (MTBE), the organic phasewas separated, washed with water, dried and freed from the solvent.After chromatography on silica gel, 6.33 g of the title compound wereobtained from the residue.

¹H NMR: 8.55 (s), 7.45 (d), 3.80 (d), 2.95 (t), 1.70 (m), 1.65 (m), 1.40(m), 0.98 (d).

Example 10 Preparation of5-methoxy-6-(2,6-difluoro-4-cyanophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine

A solution of 65 mmol of compound I-5 in 400 ml of anhydrous methanolwas, after addition of 71.5 mmol of a 30% sodium methoxide solution at20–25° C., stirred at this temperature for approximately 16 hours.Methanol was distilled off and the residue was taken up indichloromethane, then washed with water and, after drying, freed fromthe solvent. After chromatography on silica gel, 3.68 g of the titlecompound were obtained from the residue.

¹H NMR: 8.75 (s), 7.35 (d), 3.95 (s), 3.65 (d), 2.70 (t), 1.65 (m), 1.55(m), 1.45 (m), 0.95 (d).

Example 11 Preparation of5-methyl-6-(2,6-difluoro-4-cyanophenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine

A mixture of 20 ml of diethyl malonate and 0.27 g (5.65 mmol) of NaH(50% dispersion in mineral oil) in 50 ml of acetonitrile was stirred at20–25° C. for approximately 2 hours. 4.71 mmol of compound I-5 wereadded to this mixture and then the mixture was heated to approximately60° C. and stirred at this temperature for 20 hours. After addition of50 ml of aqueous NH₄Cl solution, the acidification was carried out withdilute HCl. After extracting with MTBE, the combined organic phases weredried and evaporated. The residue was purified by chromatography onsilica gel. The pure product was taken up in concentrated HCl and heldat 80° C. for 24 hours. After cooling the reaction mixture, the pH wasadjusted to 5 by addition of aqueous NaOH solution and then the mixturewas extracted with MTBE. The combined organic phases were, after drying,freed from the solvent. After chromatography on silica gel, 0.78 g ofthe title compound was obtained from the residue.

¹H NMR: 8.75 (s), 7.35 (d), 3.65 (d), 2.70 (t), 2.43 (s), 1.65 (m), 1.55(m), 1.45 (m), 0.95 (d).

Example 12 Preparation of5-chloro-6-(2,6-difluoro-4-carboxaldehydephenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine

A solution of 1.5 mmol of compound I-5 in 20 ml of dichloromethane wastreated at 0° C. with a 1M solution of 1.65 mmol of diisobutylaluminumhydride (DIBAH) in dichloromethane and was stirred at 20–25° C. for 2hours. This mixture was treated with saturated NH₄Cl solution and 10%HCl solution and the organic phase was separated and washed with water.After drying, the solvent was removed and, after chromatography onsilica gel, 0.36 g of the title compound was obtained from the residue.

¹H NMR: 10.05 (s), 8.40 (s), 7.60 (d), 3.70 (d), 2.85 (t), 1.65 (m),1.55 (m), 1.40 (m), 0.95 (d).

Example 13 Preparation of5-chloro-6-(2,6-difluoro-4-acetylphenyl)-7-(4-methylpiperidin-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine

A solution of 1.5 mmol of compound I-5 in 20 ml of tetrahydrofuran (THF)was treated, at 20–25° C., with 1.65 mmol of CuBr and a 3M solution of1.65 mmol of methylmagnesium chloride in THF and the mixture was stirredfor approximately 30 min. This mixture was treated with saturated NH₄Clsolution and 10% HCl solution and the organic phase was separated andwashed with water. After drying, the solvent was removed and, afterchromatography on silica gel, 0.22 g of the title compound was obtainedfrom the residue.

¹H NMR: 8.40 (s), 7.65 (d), 3.70 (d)., 2.80 (t), 2.70 (s), 1.70 (m),1.55 (m), 1.40 (m), 0.98 (d).

TABLE I

No. R¹ R² L¹ L² L³ L⁴ L⁵ X Phys. data (M.p. [° C.]) I-1 CH(CH₃)₂ H CN HH H H Cl 190 I-2 —(CH₂)₂CH(CH₃)(CH₂)₂— COOCH₃ F F H H Cl 8.7(s), 7.8(d),3.9(s), 3.7(d), 2.8(t), 1.6(m), 1.2(m), 0.9(d) I-3 cyclopentyl H CN H HH H Cl 207 I-4 CH(CH₃)C(CH₃)₃ H CN H H H H Cl 130 I-5—(CH₂)₂CH(CH₃)(CH₂)₂— CN F F H H Cl 8.4(s), 7.4(d), 3.7(d), 2.8(t),1.7(m), 1.4(m), 0.9(d) I-6 CH(CH₃)—CF₃ H SCH₃ F F H H Cl 174 I-7CH(CH₃)—CF₃ H SCH₃ F H F H Cl 164 I-8 CH₂CF₃ H SCH₃ F H F H Cl 161 Inthe case of chiral R¹ groups, because of the hindered rotation of thephenyl group, two diastereoisomers A) and B) may exist, which may differin their physical properties.Examples for the Action Against Harmful Fungi

The fungicidal action of the compounds of the general formula I can bedemonstrated from the following tests:

The active compounds were prepared, separately or together, as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agent with an emulsifying anddispersing action based on ethoxylated alkylphenols) and 10% by weightof Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) andwere appropriately diluted with water to the desired concentration.

Use Example 1 Activity Against Early Blight of Tomato Caused byAlternaria solani

Leaves of pot plants of the variety “Groβe Fleischtomate St. Pierre”were sprayed to runoff point with an aqueous suspension prepared from astock solution consisting of 10% of active compound, 85% ofcyclohexanone and 5% of emulsifier. On the following day, the leaveswere infected with an aqueous suspension of zoospores of Alternariasolani in 2% Biomalz solution with a concentration of 0.17×10⁶spores/ml. The plants were subsequently placed in a chamber saturatedwith water vapor at temperatures between 20 and 22° C. After 5 days,early blight in the untreated but infected control plants had soextensively developed that the infection could be visually determined in%.

In this test, the plants treated with 63 ppm of the active compound I-2of table I showed no infection, while the untreated plants were 90%infected.

Use Example 2 Activity Against Net Blotch of Barley Caused byPyrenophora teres

Leaves of pot-grown barley seedlings of the variety “Igri” were sprayedto runoff point with an aqueous preparation of active compound preparedfrom a stock solution consisting of 10% of active compound, 85% ofcyclohexanone and 5% of emulsifier. 24 hours after the spray coating haddried on, the leaves were inoculated with an aqueous suspension ofspores of Pyrenophora [syn. Drechslera] teres, the causative agent ofnet blotch. The test plants were subsequently placed in a greenhouse attemperatures of between 20 and 24° C. and a relative atmospherichumidity of 95 to 100%. After 6 days, the extent of development of thedisease was determined visually in % of infection of the total leafarea.

In this test, the plants treated with 16 ppm of the active compound I-2of table I showed 1% infection, while the untreated plants were 85%infected.

Use Example 3 Activity Against Early Blight of Tomato Caused byAlternaria solani

Pot plants of the variety “Pixie II” in the 2–4-leaf stage were sprayedto runoff point with an aqueous suspension which comprised the activecompound in the concentration given below and which was prepared from astock solution of 5% of active compound, 94% of cyclohexanone and 1% ofemulsifier (Tween 20). After the leaves had dried (3 to 5 hours), theywere infected with an aqueous suspension of zoospores of Alternariasolani comprising 0.15×10³ spores/ml. The plants were subsequentlyplaced in a chamber saturated with water vapor at temperatures between22 and 24° C. for 36 hours and then in a greenhouse at a relativehumidity of 95% at temperatures between 21 and 23° C. for 2 to 3 days.The extent of the development of infection on the leaf undersides wasthen determined visually.

In this test, the plants treated with 200 ppm of the active compoundsNo. I-6, I-7 and I-8 showed no infection in excess of 7%, while theuntreated plants were 100% infected.

Use Example 4 Activity Against Rhizoctonia solani on Rice

Pot plants of the variety “M-202” in the 2-leaf stage were sprayed torunoff point with an aqueous preparation of active compound preparedwith a stock solution of 5% of active compound, 94% of cyclohexanone and1% of emulsifier (Tween 20>). After the leaves had dried (3 to 5 hours),they were inoculated, 4 ml of an aqueous mycelium suspension ofRhizoctonia solani being pipetted onto the soil surface of each andevery pot. The plants were subsequently placed in a chamber saturatedwith water vapor at temperatures between 22 und 24° C. for 36 hours andthen in a greenhouse at a relative humidity of 95% at temperaturesbetween 21 and 23° C. for 2 to 3 days. The extent of the development ofinfection on the leaf undersides was then determined visually. The testplants were subsequently placed in climatic chambers at 18–28° C. andhigh atmospheric humidity for 4–5 days. The extent of the development ofinfection on the leaves was then determined visually.

In this test, the plants treated with 200 ppm of the active compoundsNo. I-6, I-7 and I-8 did not show more than 7% infection, while theuntreated plants were 100% infected.

1. A method for the control of harmful fungi, which comprises treatingthe fungi or the materials, plants, ground or seeds to be protected fromfungal attack with an effective amount of a triazolopyrimidine of theformula I

in which substituents have the following meanings: L¹ is cyano,S{O)_(n)A¹ or C(═O)A², wherein A¹ is hydrogen, hydroxyl, C₁–C₈-alkyl,C₁–C₈-alkylamino or di(C₁–C₈-alkyl )amino; A² is C₁–C₈-alkoxy,C₁–C₆-haloalkoxy or one of the groups mentioned under A¹; n 0, 1 or 2;L², L³ are hydrogen or halogen; L⁴, L⁵ are hydrogen, halogen orC₁–C₄-alkyl; X is halogen, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl,C₁–C₄-alkoxy or C₁–C₂-haloalkoxy; R¹ is C₁–C₈-alkyl, C₁–C₈haloalkyl,C₃–C₆cycloalkyl, C₃–C₆-halocyoloalkyl, C₂–C₈-alkenyl, C₄–C₁₀-alkadienyl,C₂–C₈-haloalkenyl, C₃–C₆-cycloalkenyl, C₂–C₈-alkynyl, C₂–C₈-haloalkynylor C₃C₆-cycloalkynyl, phenyl, naphthyl, or a five- to ten-memberedsaturated, partially unsaturated or aromatic hetero cycle, comprisingone to four heteroatoms from the group consisting of O, N and S; R² ishydrogen or one of the groups mentioned under R¹, R¹ and R² can also,together with the nitrogen atom to which they are bonded, form a five-or aix-membered ring which can be interrupted by an atom from the groupconsisting of O, N and S and/or can carry one or more subatituents fromthe group consisting of halogen, C₁–C₆-alkyl, C₁–C₆-haloalkyl andoxy-C₁–C₃-alkylenoxy or in which an N and a neighboring C atom can beconnected via a C₁C₄-alkylene chain; wherein R¹ and/or R² can besubstituted by one to four identical or different groups R^(a): R^(a) ishalogen, cyano, nitro, hydroxyl, C₁C₆-alkyl, C₁–C₆haloalkyl,C₁–C₆-alkylcarbonyl, C₃–C₆-cycioalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy,C₁–C₆-alkoxycarbonyl, C₁–C₆-alkylthio, C₁–C₆-alkylanino,di(C₁–C₆-alkyl)amino, C₂–C₆-alkenyl, C₂–C₆-alkenyloxy, C₃–C₆alkynyloxy,C₃–C₆-cycloalkyl, phenyl, naphthyl or a five- to ten-membered saturated,partially unsaturated or aromatic heterocycle, comprising one to fourheteroatoms from the group consisting of O, N and S, wherein thesealiphatic, alicyclic or aromatic groups, for their part, can bepartially or completely halogenated or can carry one to three groupsR^(b): R^(b) is halogen, cyano, nitro, hydroxyl, mercapto, amino,carboxyl, aminocarbonyl, aminothiocarbonyl, alkyl, haloalkyl, alkenyl,alkenyloxy, alkcynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,dialkylaminocarbonyl, alkylaminothiocarbonyl or dialkylamincarbonyl,wherein the alkyl groups in these radicals comprise 1 to 6 carbon atomsand the alkenyl or alkynyl groups mentioned in these radicals comprise 2to 8 carbon atoms;  and/or one to three of the following radicals: cycloalkyl, cycloalkoxy, heterocyclyl or hetarocyclyloxy, wherein thecyclic systems comprise 3 to 10 ring members; aryl, aryloxy, arylthio,aryl-C₁–C₆-alkoxy, aryl-C₁–C₆-alkyl, hetaryl, hetaryloxy or hetarylthio,wherein the aryl radicals preferably comprise 6 to 10 ring members andthe hetaryl radicals comprise 5 or 6 ring members, wherein the cyclicsystems can be partially or completely halogenated or can be substitutedby alkyl or haloalkyl groups.
 2. A triazolopyrimidine of the formula I

in which substituents have the following meanings: L¹ is cyano orC(═O)A², wherein A² is hydrogen, hydroxyl, C₁–C₈-alkyl, C₁–C₈-alkoxy,C₁C₆haloalkoxy, C₁–C₈-alkylamino or di(C₁–C₈-alkyl)amino; L², L³ arehydrogen or halogen; L⁴, L⁵ are hydrogen, halogen or C₁–C₄-alkyl; X ishalogen, cyano, C₁–C₄-alkyl, C₁–C₄-haloalkyl, C₁–C₄-alkoxy orC₁–C₂haloalkoxy; R¹ is C₁–C₈-alkyl, C₁–C₆-haloalkyl, C₃–C₆-cycloalkylC₃–C₆halocycloalkyl, C₂–C₈-alkenyl, C₄–C₁₀-alkadienyl, C₂C₈-haloalkenyl,C₃–C₆-cycloalkenyl, C₂–C₈-alkynyl, C₂C₈-haloalkynyl orC₃–C₆-cycloalkynyl, phenyl, naphthyl, or a five- to ten-memberedsaturated, partially unsaturated or aromatic heterocycle, comprising oneto four heteroatoms from the group consisting of O, N and S; R² ishydrogen or one of the groups mentioned under R¹, R¹ and R² can also,together with the nitrogen atom to which they are bonded, form a five-or six-membered ring which can be interrupted by an atom from the groupconsisting of O, N and S and/or can carry one or more substituents fromgroup consisting of halogen, C₁–C₆-alkyl, C₁–C₆-haloalkyl andoxy-C₁–C₃-alkylenoxy or in which an N and a neighboring C atom can beconnected via a C₁–C₄-alkylene chain; wherein R¹ and/or R² can besubstituted by one to four identical or different groups R^(a): R^(a) ishalogen, cyano, nitro, hydroxyl, C₁–C₆alkyl, C₁–C₆-haloalkyl,C₁–C₆-alkylcarbonyl, C₃–C₆-cycloalkyl, C₁–C₆-alkoxy, C₁–C₆-haloalkoxy,C₁–C₆-alkoxycarbonyl, C₁–C₆alkylthio, C₁–C₆-alkylamino, di(C₁–C₆-alkyl)amino, C₂–C₆-alkenyl, C₂–C₆-alkenyloxy, C₃–C₆-alkynyloxy,C₃–C₆-cycloalkyl, phenyl, naphthyl or a five- to ten-membered saturated,partially unsaturated or aromatic heterocycle, comprising one to fourheteroatoms from the group consisting of O, N and S, wherein thesealiphatic, alicyclic or aromatic groups, for their part, can bepartially or completely halogenated or can carry one to three groupsR^(b): R^(b) is halogen, cyano, nitro, hydroxyl, mercapto, amino,carboxyl, aminocarbonyl, aminocarbonyl, alkyl, haloalkyl, alkenyl,alkenyloxy, alkynyloxy, alkoxy, haloalkoxy, alkylthio, alkylamino,dialkylamino, formyl, alkylcarbonyl, alkylsulfonyl, alkylsulfoxyl,alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl,dialkylaminocarbonyl, alkylaminothiocarbonyl ordialkylaminothiocarbonyl, wherein the alkyl groups in these radicalscomprise 1 to 6 carbon atoms and the alkenyl or alkynyl groups mentionedin these radicals comprise 2 to 8 carbon atoms;  and/or one to three ofthe following radicals:  cycloalkyl, cycloalkoxy, heterocyclyl orheterocyclyloxy, wherein the cyclic systems comprise 3 to 10 ringmembers; aryl, aryloxy, arylthio, aryl-C₁–C₆-alkoxy, aryl-C₁–C₆-alkyl,hetaryl, hetaryloxy or hetarylthio, wherein the aryl radicals preferablycomprise 6 to 10 ring members and the hetaryl radicals comprise 5 or 6ring members, wherein the cyclic systems can be partially or completelyhalogenated or can be substituted by alkyl or haloalkyl groups.
 3. Acompound of the formula I as claimed in claim 2, in which L² representshalogen; L³, L⁴ represent hydrogen or halogen; and L⁵ representshydrogen.
 4. A compound of the formula I as claimed in claim 2, in whichX represents halogen.
 5. A compound of the formula I as claimed in claim2, in which R¹ and R² have the following meanings: R¹ is C₁–C₆-alkyl,C₁–C₈-haloalkyl, C₃–C₆-cycloalkyl, C₃–C₆-halocycloalkyl, C₂–C₈-alkenyl,C₂–C₈haloalkenyl, C₂–C₈-alkynyl; and R² is hydrogen or C₁–C₄-alkyl; orR¹ and R² can also, together with the nitrogen atom to which they arebonded, form a saturated or unsaturated 5- or 6-membered ring which cancarry one or two substituents from the group consisting of halogen,C₁–C₆-alkyl and C₁–C₆-haloalkyl.
 6. A process for the preparation of thecompounds of the formula I as claimed in claim 2 in which X is halogen,cyano, C₁–C₄-alkoxy or C₁–C₂-haloalkoxy, by reaction of 5-aminotriazoleof the formula II

with phenylmalonates of the formula III,

to give dihydroxytriazolopyrimidines of the formula IV

and halogenation to give the dihalogen compounds of the formula V,

in which Y is halogen, reaction with amines of the formula VI,

in which R¹ and R² have the meanings given in claim 2, to give5-halo-7-aminotriazolopyrimidines of the formula I in which X ishalogen, and, for the preparation of compounds of the formula I in whichX represents cyano, C₁–C₄-alkoxy or C₁–C₂-haloalkoxy, reaction withcompounds of the formula VII,M-X′  VII which, according to the meaning of the group X′ to beintroduced, represents an inorganic cyanide, alkoxide or haloalkoxideand in which M is an ammonium, tetraalkylammonium, alkali metal oralkaline earth, metal cation.
 7. A process for the preparation of thecorn pounds of the formula I as claimed in claim 2 in which X isC₁–C₄-alkyl, by reaction of 5-aminotriazole of the formula II

with dicarbonyl compounds of the formula IIIa,

in which R and X¹ are C₁–C₄-alkyl, to give hydroxytriazolopyrimidines ofthe formula IVa

halogenation to give compounds of the formula Va

in which Y is halogen, and reaction with amines of the formula VI

in which R¹ and R² have the meanings given in claim 2, to givetriazolopyrimidines of the formula I in which X is C₁–C₄alkyl.
 8. Acomposition suitable for the control of harmful fungi, comprising asolid or liquid carrier and a compound of the formula I as claimed inclaim
 2. 9. A method for the control of harmful fungi, which comprisestreating the fungi or the materials, plants, ground or seeds to beprotected from fungal attack with an effective amount of a compound ofthe formula I as claimed in claim
 2. 10. A compound of the formulaeIIIa, IV, IVa, V and Va

wherein R is C₁–C₄-alkyl; X¹ is C₁–C₄-alkyl; Y is halogen; L¹ is cyano,or C(═O)A², wherein A² is C₁–C₈-alkoxy, C₁–C₆hydroxylkoxy, hydrogen,hydroxyl, C₁–C₈-alkyl, C₁–C₈-alkylamino or di(C₁–C₈-alkyl)amino; L², L³are hydrogen or halogen; and L⁴, L⁵ are hydrogen, halogen or C₁–C₄alkyl.